Polyurethane composition

ABSTRACT

The present technology provides a polyurethane composition including: a main agent; and a curing agent, wherein the main agent includes a urethane prepolymer having an isocyanate group, a morpholine compound having one morpholine ring, and an ether compound having two dimethylamino groups, and the curing agent includes an active hydrogen compound having two or more active hydrogen-containing groups in one molecule.

TECHNICAL FIELD

The present technology relates to a polyurethane composition.

BACKGROUND ART

In the related art, a polyurethane composition has been used as a sealing agent, an adhesive, and the like for automobile, construction, and structure.

Japan Unexamined Patent Publication No. 2001-348416 aims to provide a moisture-curable polyurethane composition which has excellent adhesion to glass, metal, plastic, painted steel sheet, or the like without using a primer, and also has excellent curability and storage stability, and discloses a moisture-curable polyurethane composition including (A) a urethane prepolymer, (B) at least one silane compound selected from the group consisting of (B-1) a silane compound obtained by adding a compound, to which an aromatic ring or a derivative thereof are directly bonded, to a reactant of at least one selected from the group consisting of xylene diisocyanate, 1,3- or 1,4-di(isocyanatemethyl) cyclohexane, and derivatives thereof with three or more active hydrogens and a nitrogen atom in a secondary aminoalkoxysilane and (B-2) a silane compound having a lysine skeleton obtained by adding a compound to which an aromatic ring or derivatives thereof are directly bonded, to a lysine isocyanate having two or three isocyanate groups and a nitrogen atom in a secondary aminoalkoxysilane, (C) at least one type of a tertiary amine-based catalyst having a morpholine structure and/or a dimethylamino group structure, and (D) an organotin-based compound.

In such a case, the present inventors have found, by referring to Japan Unexamined Patent Publication No. 2001-348416, that as a result of preparing a composition which includes a main agent including a urethane prepolymer and at least one type of a tertiary amine-based catalyst having a morpholine structure and/or a dimethylamino group structure and a curing agent and evaluating the composition, long-term adhesion of the composition against weather resistance and vibration may be degraded.

SUMMARY

The present technology provides a polyurethane composition excellent in long-term adhesion against weather resistance and vibration.

As a result of intensive studies, the present inventors have found that desired effects are obtained in a polyurethane composition comprising a main agent; and a curing agent, the main agent includes a urethane prepolymer having an isocyanate group, a morpholine compound having one morpholine ring, and an ether compound having two dimethylamino groups, and the curing agent includes an active hydrogen compound having two or more active hydrogen-containing groups in one molecule.

The present technology provides the following features.

1. A polyurethane composition includes: a main agent; and a curing agent, in which the main agent includes a urethane prepolymer having an isocyanate group, a morpholine compound having one morpholine ring, and an ether compound having two dimethylamino groups, and the curing agent includes an active hydrogen compound having two or more active hydrogen-containing groups in one molecule.

2. In the polyurethane composition described in the above 1, a content of the morpholine compound is from 0.02 to 1.6 parts by mass with respect to 100 parts by mass of the urethane prepolymer, and a content of the ether compound is from 0.002 to 0.16 parts by mass with respect to 100 parts by mass of the urethane prepolymer.

3. In the polyurethane composition as described in the above 1 or 2, the morpholine compound is dimethylaminoethyl morpholine.

4. In the polyurethane composition described in any one of the above 1 to 3, the ether compound is bis(dimethylaminoethyl) ether.

5. In the polyurethane composition described in any one of the above 1 to 4, the main agent further includes at least one organophosphorus compound selected from the group consisting of a phosphite compound, a phosphonite compound, a phosphinite compound, and a phosphine compound.

6. In the polyurethane composition described in the above 5, a content of the organophosphorus compound is from 0.01 to 1.0 part by mass with respect to 100 parts by mass of the urethane prepolymer.

7. In the polyurethane composition as described in the above 5 or 6, the organophosphorus compound is triphenylphosphine.

8. In the polyurethane composition as described in any one of the above 1 to 7, the active hydrogen compound contains at least a tetravalent hydroxy compound having 4 hydroxy groups in one molecule.

9. In the polyurethane composition as described in any one of the above 1 to 8, a hydroxyl value of the active hydrogen compound is 200 to 500 mg KOH/g.

10. In the polyurethane composition described in any one of the above 1 to 9, a content of the active hydrogen compound is from 0.2 to 2 parts by mass with respect to 100 parts by mass of the urethane prepolymer.

The polyurethane composition according to the embodiment of the present technology has excellent long-term adhesion against weather resistance and vibration.

In the present specification, the long-term adhesion against the weather resistance and vibration may be referred to as adhesion.

DETAILED DESCRIPTION

Embodiments of the present technology are described in detail below.

Note that in the present specification, numerical ranges indicated using “(from) . . . to . . . ” include the former number as the lower limit value and the latter number as the upper limit value.

In the present specification, unless otherwise noted, a single corresponding substance may be used for each component, or a combination of two or more types of corresponding substances may be used for each component. When a component contains two or more types of substances, the content of the component means the total content of the two or more types of substances.

In the present specification, it is said that the effect of the present technology is more excellent in the long-term adhesion against the weather resistance and vibration.

Polyurethane Composition

A urethane composition according to the embodiment of the present technology (composition according to the embodiment of the present technology) is a polyurethane composition including: a main agent; and a curing agent, in which the main agent includes a urethane prepolymer having an isocyanate group, a morpholine compound having one morpholine ring, and an ether compound having two dimethylamino groups, and the curing agent includes an active hydrogen compound having two or more active hydrogen-containing groups in one molecule.

The composition according to an embodiment of the present technology is thought to achieve desired effects as a result of having such a configuration. The inventors infer the reason as follows.

The inventors consider that a material (a composition containing a urethane prepolymer) having high thixotropy is excellent in bead moldability, but is hardly wetted to a base material (adherend) and has low adhesion.

In addition, the present inventors consider that a difference in catalytic activity between compounds having a morpholine ring affects the adhesion.

In general, a compound having a plurality of (two or more) morpholine rings (polymorpholine compounds) has higher catalytic activity for a urethane prepolymer than a morpholine compound (monomorpholine compound) having one morpholine ring.

For this reason, when a composition containing the urethane prepolymer and a filler (for example, carbon black and the like) contains a polymorpholine compound, the polymorpholine compound tends to coordinates to the urethane prepolymer due to the high catalytic activity and the urethane prepolymer after the coordination has steric hindrance due to the morpholine ring, so the polymorpholine compound becomes difficult to access the filler. Thus, it is considered that the composition containing the polymorpholine compound is hardly wetted to the filler.

Here, when the filler is considered to be replaced with a base material (adherend), the composition is considered to be difficult to be wetted to the base material (adherend) and to have the low adhesion.

In addition, the present inventors estimate that an addition amount of the morpholine compound is small due to the high catalytic activity and thus the wettability is lowered.

On the other hand, when the composition containing the urethane prepolymer and the filler contains the monomorpholine compound, the monomorpholine compound has the lower catalytic activity than the polymorpholine compound, and its action on the urethane prepolymer is alleviated, whereas the urethane prepolymer is less affected by the steric hindrance due to the morpholine ring and tends to act on the filler. Thus, it is considered that the composition containing the monomorpholine compound is hardly wetted to the filler.

Here, when the filler is considered to be replaced with the base material (adherend), the composition is considered to be easily wetted to the base material (adherend) and to have the excellent adhesion.

In addition, the addition amount of the monomorpholine compound can be large due to the low catalytic activity described above. For this reason, the composition is considered to be easily wetted or more wetted to the filler and the base material.

In addition, since the composition according to the embodiment of the present technology contains an ether compound having two dimethylamino groups having the smaller steric hindrance than the morpholine ring in addition to the morpholine compound having the one morpholine ring, the composition is estimated to be wetted to the filler and the base material.

Thus, the composition according to the embodiment of the present technology is considered to have the excellent adhesion by using the morpholine compound having one morpholine ring and the ether compound having two dimethylamino groups in combination as a catalyst.

Each of the components contained in the composition according to an embodiment of the present technology will be described in detail below.

Main Agent

In the embodiment of the present technology, the main agent includes a urethane prepolymer having an isocyanate group, a morpholine compound having one morpholine ring, and an ether compound having two dimethylamino groups.

Urethane Prepolymer

In the composition according to the embodiment of the present technology, the main agent includes a urethane prepolymer having an isocyanate group.

An example of a preferable aspect is one in which the urethane prepolymer has an isocyanate group at a terminal thereof.

One molecule of the urethane prepolymer preferably has a plurality of isocyanate groups, and more preferably two isocyanate groups.

A content of the isocyanate group is preferably from 0.5 to 5% by mass with respect to a total amount of the urethane prepolymer.

The polyisocyanate used during production of the urethane prepolymer is not particularly limited as long as the polyisocyanate has two or more isocyanate groups in each molecule.

Examples of the polyisocyanate used in the production of the urethane prepolymer include aromatic polyisocyanates such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI; for example, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate), 1,4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate (XDI), tetramethyl xylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), and triphenylmethane triisocyanate;

aliphatic polyisocyanates (including alicyclic polyisocyanates) such as hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI), transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), bis(isocyanatemethyl) cyclohexane (H₆XDI), and dicyclohexylmethane diisocyanate (H₁₂MDI);

carbodiimide-modified polyisocyanates thereof; and

isocyanurate modified polyisocyanates thereof.

The polyisocyanate is preferably an aromatic polyisocyanate and more preferably an MDI from the perspective of excellent curability.

The compound having two or more active hydrogen-containing groups per molecule (active hydrogen compound) that is used during production of the urethane prepolymer is not particularly limited. Examples of the active hydrogen-containing group include a hydroxy (OH) group, an amino group, and an imino group.

Preferred examples of an active hydrogen compound include a polyol compound and the like having two or more hydroxyl (OH) group in 1 molecule, and among those, a polyol compound is preferable.

The polyol compound used in the production of the urethane prepolymer is not particularly limited as long as the polyol compound is a compound having two or more hydroxy groups. Examples thereof include polyether polyols; polyester polyols; polymer polyols having a carbon-carbon bond in a main chain backbone, such as acrylic polyols, polybutadiene diols, and hydrogenated polybutadiene polyols; low molecular weight polyhydric alcohols; and mixed polyols of these. Among these, a polyether polyol is exemplified as an example of preferable aspects.

The polyether polyol is not particularly limited as long as the polyether polyol is a compound having a polyether as a main chain and having two or more hydroxy groups. The polyether is a group having two or more ether bonds, and specific examples thereof include a group having a total of two or more structural units —R^(a)—O—R^(b)—. Here, in the structural units, R^(a) and R^(b) each represent a hydrocarbon group independently. The hydrocarbon group is not limited. Examples thereof include a linear alkylene group having from 1 to 10 carbon atoms.

Examples of the polyether polyol include a polyoxyethylene diol (polyethylene glycol), polyoxypropylene diol (polypropylene glycol; PPG), polyoxypropylene triol, ethylene oxide/propylene oxide copolymer, polytetramethylene ether glycol (PTMEG), polytetraethylene glycol, sorbitol polyol, and the like.

The polyether polyol is preferably polypropylene glycol or polyoxypropylene triol from the perspective of excellent miscibility with polyisocyanate.

A weight average molecular weight of the polyether polyol is preferably from 500 to 20000 from the viewpoint that a viscosity of the urethane prepolymer obtained by the reaction with the isocyanate can have appropriate fluidity at a normal temperature. In the present technology, the weight average molecular weight is a value obtained by GPC analysis (solvent: tetrahydrofuran (THF)) based on calibration with polystyrene.

From the viewpoint that the adhesion and curability are more excellent, the urethane prepolymer is preferably a urethane prepolymer obtained by reacting a polyether polyol with an aromatic polyisocyanate, and more preferably a urethane prepolymer obtained by reacting at least one selected from the group consisting of polyoxypropylene diol and polyoxypropylene triol with diphenylmethane diisocyanate.

The urethane prepolymer can be used alone or in combination of two or more kinds.

The method of producing the urethane prepolymer is not particularly limited. For example, the urethane prepolymer can be produced by using polyisocyanate in a manner that from 1.5 to 2.5 mol of isocyanate group is reacted per 1 mol of the active hydrogen-containing group (e.g. hydroxy group) contained in the active hydrogen compound, and mixing these to perform a reaction.

Morpholine Compound

The morpholine compound contained in the main agent in the composition according to the embodiment of the present technology has one morpholine ring.

Preferably, a hydrocarbon group which may have a hetero atom is bonded to the nitrogen atom of the morpholine ring.

The hydrocarbon group is not limited. Examples of the hydrocarbon group include an aliphatic hydrocarbon group (including linear, branched, and alicyclic types), an aromatic hydrocarbon group, and a combination thereof.

Examples of the hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom.

An example of a preferable aspect is one in which the nitrogen atom constituting the morpholine compound forms a tertiary amine.

Examples of the morpholine compound include a compound represented by Chemical Formula (1) below.

In Chemical Formula (1) above, R₁, R₂, and R₃ each represent a hydrocarbon group independently.

R₁ is preferably an alkylene group having 1 to 8 carbon atoms, and more preferably an ethylene group.

R₂ is preferably an alkylene group having 1 to 3 carbon atoms, and more preferably a methyl group. The same goes for R₃.

As the morpholine compound, dimethylaminoethyl morpholine is preferable from the viewpoint that the effect of the present technology is excellent, yarn breakage property is excellent, and balance between the catalytic activity and the yarn breakage property is good.

Content of Morpholine Compound

The content of the morpholine compound is preferably from 0.02 to 1.6 parts by mass and more preferably from 0.3 to 1.0 part by mass with respect to 100 parts by mass of a urethane prepolymer, from the viewpoint that the effect of the present technology is excellent, a curing rate falls within an appropriate range, or yarn breakage property or storage stability is excellent.

Ether Compound

In the composition according to the embodiment of the present technology, the ether compound contained in the main agent is a compound having two dimethylamino groups and having an ether bond.

The ether compound does not contain the morpholine compound.

A dimethylamino group can be bonded to a hydrocarbon group bonded to an oxygen atom constituting an ether bond. The hydrocarbon group is not limited. Examples of the hydrocarbon group include an aliphatic hydrocarbon group (including linear, branched, and alicyclic types), an aromatic hydrocarbon group, and a combination thereof. Examples of the aliphatic hydrocarbon group include a (linear) alkylene group having 1 to 10 carbon atoms.

Examples of the ether compound include a compound represented by Chemical Formula (2) below.

In Chemical Formula (2) above, R₄ and R₅ each represent the hydrocarbon group independently.

R₄ is preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an ethylene group. The same goes for R₅.

The ether compound is preferably bis(dimethylaminoethyl) ether from the viewpoint that the effect of the present technology is excellent, the catalytic activity is high, and the yarn breakage property is excellent only with a small amount of addition.

Content of Ether Compound

The content of the ether compound is preferably from 0.002 to 0.16 parts by mass and more preferably from 0.008 to 0.10 parts by mass with respect to 100 parts by mass of the urethane prepolymer from the viewpoint that the effect of the present technology is excellent and the yarn breakage property is excellent.

Content of Morpholine Compound and Ether Compound

Preferably, the content of the morpholine compound: x parts by mass and the content of the ether compound: y parts by mass, which are used with respect to 100 parts by mass of the urethane prepolymer, satisfy Chemical Formula (3) below, from the viewpoint that the effect of the present technology is excellent and the yarn breakage property, the curing rate, or the storage stability is excellent. An upper limit of x+10y is more preferably 1.7 or less from the viewpoint of the excellent yarn breakage property. A lower limit of x+10y is more preferably 0.23 or more from the viewpoint of the excellent curing rate. 0.2≤x+10y≤1.8  (3)

In Chemical Formula (3) above, x and y are both greater than 0.

Organophosphorus Compound

In the composition according to the embodiment of the present technology, the main agent is at least one organophosphorus compound selected from the group consisting of a phosphite compound, a phosphonite compound, a phosphinite compound, and a phosphine compound, and more preferably the phosphine compound from the viewpoint of the excellent yarn breakage property.

An organic group of the organophosphorus compound is not particularly limited to including a phosphorus atom. Examples of the organic group include an oxygen atom, a hydrocarbon group and a combination thereof. The hydrocarbon group is not limited. Examples of the hydrocarbon group include an aliphatic hydrocarbon group (including linear, branched, and alicyclic types), an aromatic hydrocarbon group, and a combination thereof.

A hydrogen atom may be further bonded to the phosphorus atom of the organophosphorus compound, in addition to the organic group.

Phosphine Compounds

In the present specification, the phosphine compound means a compound in which at least one or all of hydrogen atoms of PH₃ are substituted with a hydrocarbon group.

Examples of the phosphine compound include: a phosphine compound in which three aromatic hydrocarbon groups are bonded to a phosphorus atom, such as triphenylphosphine (TPP), triorthotolylphosphine, trimetatolylphosphine, triparatolylphosphine, tris-4-methoxyphenylphosphine;

a phosphine compound having one phosphorus atom in one molecule and three aromatic hydrocarbon groups and three aliphatic hydrocarbon groups in the phosphorus atom, such as diphenylcyclohexylphosphine, dicyclohexylphenylphosphine, and tricyclohexylphosphine;

phosphine compounds having three aliphatic hydrocarbon groups in the phosphorus atom, such as trioctylphosphine and tributylphosphine;

a phosphine compound having a plurality of phosphorus atoms in one molecule, such as 1,2-bis(diphenylphosphino) ethane, 1,3-bis(diphenylphosphino) propane, and 1,4-bis(diphenylphosphino) butane, and the like.

Among those, the phosphine compound is preferably a phosphine compound having at least an aromatic hydrocarbon group, more preferably a phosphine compound in which three aromatic hydrocarbon groups are bonded to a phosphorus atom, and still more preferably triphenylphosphine, from the viewpoint of the excellent yarn breakage property.

Content of Organophosphorus Compound

The content of the organophosphorus compound is preferably from 0.01 to 1.0 part by mass and more preferably from 0.08 to 0.8 parts by mass with respect to 100 parts by mass of the urethane prepolymer from the viewpoint that the effect of the present technology is excellent and the yarn breakage property is excellent.

Tertiary Amine

The main agent can further include a tertiary amine.

The tertiary amine does not include the morpholine compound and the ether compound.

The tertiary amine is a compound in which three hydrocarbon groups are bonded to one nitrogen atom.

Examples of the tertiary amine include trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, trihexylamine, trioctylamine, trilaurylamine, dimethylethylamine, dimethylpropylamine, dimethylbutylamine, dimethylamylamine, dimethylhexylamine, dimethylcyclohexylamine, dimethyloctylamine, dimethyllaurylamine, triallylamine, tetramethylethylenediamine, triethylenediamine, 1,8-diazabicyclo [5.4.0] undecene-1,1,4-diazabicyclo [2.2.2] octane, triethanolamine, N,N′-dimethylpiperazine, tetramethyl butanediamine, bis(2,2-morpholinoethyl) ether, and the like.

Preferably, the content of the tertiary amine is [(x+10y)/2] parts by mass or less with respect to 100 parts by mass of the urethane prepolymer, from the viewpoint that the effect of the present technology is excellent and the balance between curability, storage stability, and workability is excellent.

In the (x+10y)/2, x is the content (parts by mass) of the used morpholine compound with respect to 100 parts by mass of the urethane prepolymer.

In the (x+10y)/2, y is the content (parts by mass) of the used ether compound with respect to 100 parts by mass of the urethane prepolymer.

Metal Catalyst

The main agent can further contain a metal catalyst.

The metal catalyst is not particularly limited as long as the metal catalyst is a compound capable of promoting the reaction of the isocyanate group. Examples of the metal catalyst include an organometallic catalyst and a metal catalyst (also referred to as an inorganometallic catalyst) made of only a metal having no organic group.

Examples of the metal included in the metal catalyst include tin, bismuth, titanium, and the like.

The organic group included in the organometallic catalyst is not particularly limited. Examples of the organometallic catalyst include metal carboxylates, alkoxides, and complexes. Examples of the organometallic catalyst can include at least one selected from the group consisting of a carboxylate ion, an alkyl group, a carboxylic acid, an alkoxy group, and a ligand. The carboxylate ion, the alkyl group, the carboxylic acid, the alkoxy group, and the ligand are not particularly limited.

Preferably the metal catalyst includes an organotin catalyst.

Examples of the organotin catalyst include carboxylates of tin such as dioctyltin dilaurate, dibutyltin dilaurate, dibutyltin maleate, first tin octoate, dibutyltin diacetylacetonate, and dioctyltin maleate; a reactant obtained by reacting 1,3-diacetoxy-1,1,3,3-tetrabutyl-distannoxane with ethyl silicate so that a molar ratio is from 1:0.8 to 1:1.2, and the like.

The content of the metal catalyst is preferably from 0.001 to 1.0 part by mass and more preferably from 0.008 to 0.08 parts by mass with respect to 100 parts by mass of the urethane prepolymer in that the effect of the present technology is excellent.

Curing Agent

The composition according to the embodiment of the present technology has a curing agent.

The composition according to the embodiment of the present technology can accelerate the curing rate of the composition by having the curing agent.

The curing agent contained in the composition according to the embodiment according to the present technology includes an active hydrogen compound having two or more active hydrogen-containing groups in one molecule.

The curing agent contained in the composition according to the embodiment of the present technology is a curing agent in a broad sense, and the active hydrogen compound contained in the curing agent is a component (curing agent in a narrow sense) for curing the urethane prepolymer contained in the above-described main agent.

Active Hydrogen Compound

In the embodiment of the present technology, the active hydrogen compound is a compound having two or more active hydrogen-containing groups in one molecule.

Examples of the active hydrogen-containing group include a hydroxyl (OH) group, an amino group and an imino group. Among those, the OH group (hydroxy group) is preferable.

Skeleton of Active Hydrogen Compound

Examples of the skeleton of the active hydrogen compound include: polyether; polyester; polybutadiene; rosin, and the like.

The active hydrogen-containing group can be bonded to the skeleton.

The skeleton of the active hydrogen compound may have a structure derived from an initiator used in producing the active hydrogen compound.

The initiator used in producing the active hydrogen compound is not particularly limited. Examples of the initiator include: an amine compound having a plurality of amino groups such as ethylene diamine; and a hydroxy compound having a plurality of hydroxy groups such as sorbitol.

In the initiator, an active group as the initiator such as the amino group or the hydroxy group can be bonded to a hydrocarbon group. The hydrocarbon group is not limited. Examples of the hydrocarbon group include an aliphatic hydrocarbon group (including linear, branched, and alicyclic types), an aromatic hydrocarbon group, and a combination thereof.

Number of Active Hydrogen-Containing Groups

The number of active hydrogen-containing groups which the active hydrogen compound has in one molecule is preferably from 4 to 6, and more preferably 4 and 5.

Among those, preferably, the active hydrogen compound contains at least a tetravalent hydroxy compound having four hydroxy groups in one molecule, from the viewpoint that the effect of the present technology is excellent, the curing rate is rapid, or balance between the curing rate and a pot life is excellent.

In the tetravalent hydroxy compound, the hydroxy group is preferably bonded to the hydrocarbon group which may have a nitrogen atom and/or an oxygen atom.

Examples of the hydrocarbon group include an aliphatic hydrocarbon group (including linear, branched, and alicyclic types), an aromatic hydrocarbon group, and a combination thereof.

An example of a preferable aspect is one in which the skeleton of the tetravalent hydroxy compound is a polyether. Examples of the skeleton of the tetravalent hydroxy compound may include a nitrogen atom or an oxygen atom derived from the initiator. When the nitrogen atom is bonded to three carbon atoms, the nitrogen atom can form a tertiary amine. When the oxygen atom is bonded to two carbon atoms, the oxygen atom can form an ether bond.

Examples of the tetravalent hydroxy compound include an aliphatic hydrocarbon compound which may have four hydroxy groups and have a nitrogen atom or an oxygen atom.

Examples of the tetravalent hydroxy compound include a compound represented by Chemical Formula (4) below.

In Chemical Formula (4) above, R₆ to R₁₀ each represent a hydrocarbon group independently, and a to d each represent 1 to 10 independently.

Each of R₆ to R₉ preferably represents an alkylene group independently, and more preferably an alkylene group having 1 to 18 carbon atoms. The alkylene group may be any of linear, branched or cyclic types. Specifically, examples of the alkylene group include an ethylene group, a trimethylene group, and a propylene group.

R₁₀ is preferably an alkylene group having 1 to 8 carbon atoms. The alkylene group may be any of linear, branched or cyclic types. Specifically, examples of the alkylene group include an ethylene group, a trimethylene group, and a propylene group.

Each of a to d preferably represents 2 to 6 independently.

The hydroxyl value of the active hydrogen compound (for example, the tetravalent hydroxy compound) is preferably from 200 to 500 mg KOH/g, and more preferably from 300 to 480 mg KOH/g, from the viewpoint that the effect of the present technology is excellent, the curing rate is rapid, or the hardness of the cured product obtained by curing the composition according to the embodiment of the present technology is hardly reduced.

In the embodiment of the present technology, the hydroxyl value was measured according to JIS (Japanese Industrial Standard) K1557-1:2007.

A method for producing an active hydrogen compound is not particularly limited. Examples thereof include known products.

The content of the active hydrogen compound is preferably from 0.1 to 2 parts by mass and more preferably from 0.2 to 1.8 parts by mass with respect to 100 parts by mass of the urethane prepolymer, from the viewpoint that the effect of the present technology is excellent, the curing rate is rapid, or the balance between the curing rate and the pot life is excellent.

Additives

The composition according to the embodiment of the present technology may further contain an additive, as needed, as long as the technology is not impaired. Examples of the additives include: a filler such as carbon black or calcium carbonate; a plasticizer such as diisononyl phthalate; a surface lubricant, a leveling agent, an antioxidant, a corrosion inhibitor, a light stabilizer, an ultraviolet absorber, a thixo imparting agent, and the like. The type and content of the additive can be selected appropriately.

The content of the filler is preferably from 10 to 120 parts by mass with respect to 100 parts by mass of the urethane prepolymer.

The content of the plasticizer is preferably from 5 to 100 parts by mass with respect to 100 parts by mass of the urethane prepolymer.

The additives can be added to one or both of the main agent and the curing agent.

An example of the preferable aspects is one in which the composition according to the embodiment of the present technology does not substantially contain a compound having a plurality of morpholine rings in one molecule.

The fact that the composition according to the embodiment of the present technology does not substantially contain the compound having the plurality of morpholine rings means that the content of the compound having the plurality of morpholine rings is from 0 to 0.01 parts by mass with respect to 100 parts by mass of the urethane prepolymer.

Production Method

A production method of a composition according to the embodiment of the present technology is not particularly limited. For example, the main agent can be prepared by a method in which the urethane prepolymer, the morpholine compound, and the ether compound are sufficiently mixed in a nitrogen gas atmosphere.

As necessary, each optional component may be added to one or both of the main agent and the curing agent. When the curing agent further contains optional components, the curing agent can be prepared by being sufficiently mixed under the nitrogen gas atmosphere as in the preparation of the main agent.

The composition according to the embodiment of the present technology has at least the main agent and the curing agent. The composition according to the embodiment of the present technology may further have agents other than the main agent and the curing agent.

The composition according to the embodiment of the present technology is preferably a two-component polyurethane composition having only the main agent and the curing agent.

Method of Use

When the composition of this technology is used, the main agent and the curing agent can be mixed, and the obtained mixture can be used as the composition according to the embodiment of the present technology.

The composition according to the embodiment of the present technology can be cured, for example, under conditions of −20° C. to +50° C.

In the embodiment according to the present technology, the polyurethane of the “polyurethane composition” means polyurethane in a broad sense, that is, a compound derived from an isocyanate group.

Examples of the use of the composition according to an embodiment of the present technology include an adhesive.

The adherend (base material) to which the composition of the technology can be applied is not particularly limited. Examples of the adherend include metal (including a coated sheet and an electrodeposition-coated steel sheet), plastic, rubber and glass.

As necessary, a primer may be used for the adherend. The primer is not particularly limited. Examples of the primer include a composition containing a compound having a hydrolyzable silyl group such as an isocyanate group and/or an alkoxysilyl group.

The composition according to the embodiment of the present technology can be used as an adhesive of a vehicle body and a window glass; and an adhesive of parts such as a rocket pin and a hinge and a window glass.

EXAMPLES

The present technology is described below in detail using examples but the present technology is not limited to such examples.

Production of Composition

Each component shown in a column of the main agent of Table 1 was mixed in the composition (parts by mass) shown in Table 1 using a stirrer, such that the main agent was prepared.

Then, the composition was prepared by mixing the main agent prepared as described above with the curing agent shown in the column of the curing agent in Table 1 in the compositions (parts by mass) shown in Table 1 using the stirrer.

The amount of the urethane prepolymer in Table 1 is the net amount of the urethane prepolymer.

Evaluation

The following evaluations were performed by using the composition produced as described above. The results are shown in Table 1.

Adhesion

Production of Evaluation Sample

One glass (25 mm long×100 mm wide×0.8 mm thick) was prepared as an adherend. Each composition produced as described above was applied to the glass at a room temperature. A cationic electrodeposition-coated steel sheet (trade name GT-10LF for electrodeposition paint, available from Kansai Paint Co., Ltd. No primary) overlaps the glass to crimp both the adherends. A length of a joint (portion where the electrodeposition-coated steel sheet and the glass overlap each other) between the electrodeposition-coated steel sheet and the glass was 10 mm. The thickness of the composition at the joint was 5 mm. After the crimping, the sample for evaluation was produced under conditions of 20° C. and 65% RH for 7 days.

Cycle/Vibration Composite Test

Cycle Test

First, using each of the samples for evaluation produced as described above, a cycle test was performed by repeating the following series of conditions A for 20 cycles.

Series of Conditions A

First, each of the samples for evaluation was placed under conditions of −30° C. for 3 hours, under conditions of 20° C. and 65% RH for 0.5 hours, and then under conditions of 100° C. for 20 hours, and finally, was placed under conditions of 20° C. and 65% RH for 0.5 hours. The above is referred to as a series of conditions A. The series of conditions A is one cycle.

Vibration Test

The sample for evaluation after the cycle test was subjected to a vibration test in which vibration was applied 1 million times under the conditions of a shear stress of 150 N and a frequency of 10 Hz.

Tensile Shear Test

A tensile shear test was performed under the conditions of a tensile speed of 200 mm/min and 20° C. according to JIS K 6850:1999 using each of the samples for evaluation after the vibration test.

Evaluation Criteria of Adhesion

In each of the evaluation samples after the tensile shear test, the case where the adhesive (the portion where the composition is cured) is cohesively broken was evaluated as excellent in adhesion (long-term adhesion to weather resistance and vibration), which was represented by “good”.

In each of the samples for evaluation, when the adhesive is not cohesively broken (for example, when the adhesive breaks the interface in the evaluation sample or when the samples for evaluation is broken during the vibration test), the adhesion was evaluated to be poor, which was displayed as “poor”.

As described above, in the cycle/vibration composite test, a wide temperature range of −30° C. to +100° C., conditions assuming rainfall at 20° C. and 65% RH and the like are set in the cycle test, and the cycle test and the vibration test are combined, such that the cured product of the composition was exposed to various weather resistance and vibrations for a long time outdoors.

In addition, the adhesion after the cycle/vibration composite test was also evaluated as the long-term adhesion to weather resistance and vibration.

Yarn Breakage Property

Discharge Test

Each composition produced as described above was heated to 35° C. and charged into a robot coating apparatus. A robot coating apparatus has a nozzle, and the nozzle has a cut portion (the shape of the cut portion is an isosceles triangle with a bottom side of 8 mm and a height of 12 mm) on a side surface of a tip thereof.

Each of the compositions heated is discharged from the cut portion to the base material at a speed of 2000 g/min while moving the nozzle at a speed of 300 mm/min on the base material, and each of the compositions is imparted to the base material. The composition was imparted to the base material by means of the nozzle in the form of a triangular prism having an isosceles triangle with a bottom side of 8 mm and a height of 12 mm as a cross section.

After the discharge started, the discharge of the composition from the nozzle was stopped and the movement of the nozzle was continued as described above.

After the discharge of the composition from the nozzle was stopped, the movement of the nozzle was continued until a composition between the composition imparted to the base material and the nozzle was yarn-broken.

Measurement of Length of Composition Remaining on Tip of Nozzle

After the composition was yarn-broken, the movement of the nozzle was stopped.

After the movement of the nozzle was stopped, the length of the composition (from the cut portion of the nozzle to the tip of the composition) was measured at the tip of the nozzle. When the tip of the composition remaining on the tip of the nozzle is curled, the composition coming out of the cut portion and the nozzle are seen from the side, and the length of the composition coming out from the cut portion of the nozzle was measured along a center line of the composition coming out from the cut portion.

Evaluation Criteria of Yarn Breakage Property

When the measured length was 30 mm or less, the yarn breakage property was evaluated to be very excellent, which was represented by “good”.

When the length exceeds 30 mm but is less than 50 mm, the yarn breakage property was evaluated to be somewhat excellent, which is represented by “fair”.

When the length exceeds 50 mm, the yarn breakage property was evaluated to be poor, which is represented by “poor”.

By achieving the excellent yarn breakage property, the composition adheres to a portion of the base material on which the application of the composition is not required and thus the base material is not contaminated with the composition and the workability is excellent.

Curing Rate

Production of Sample for Curing Rate Evaluation

One glass (25 mm long×100 mm wide×0.8 mm thick) was prepared as an adherend. Each composition produced as described above was applied to the glass at a room temperature. An electrodeposition-coated steel sheet (trade name GT-10LF for paint, available from Kansai Paint Co., Ltd. No primary) overlaps the glass to crimp both the adherends. A length of a joint (portion where the electrodeposition-coated steel sheet and the glass overlap each other) between the electrodeposition-coated steel sheet and the glass was 10 mm. The thickness of the composition at the joint was 5 mm. After the crimping, the sample for curing rate evaluation was produced under conditions of 20° C. and 65% RH for 30 minutes.

Tensile Shear Test

A tensile shear test was performed under the conditions of a tensile speed of 200 mm/min and 20° C. according to JIS K6850:1999 using each of the samples for curing rate evaluation as described above to measure shear strength.

Evaluation Criteria of Curing Rate

When the shear strength was 0.3 MPa or more, it was evaluated that the curing rate was fast and the curing rate was excellent, which was represented by “good”.

When the shear strength was 0.21 MPa or more and less than 0.3 MPa, it was evaluated that the curing rate was slightly fast and the curing rate was slightly poor, which was represented by “fair”.

When the shear strength was less than 0.21 MPa, it was evaluated that the curing rate was slow and that curing rate was poor, which was represented by “poor”.

Pot Life

Production of Sample for Pot Life Evaluation

A primer (trade name M (RC-50E), available from Yokohama Rubber Co., Ltd.) was applied to an electrodeposition-coated steel sheet (paint: GT-10LF, Kansai Paint Co., Ltd.).

On the other hand, each composition produced as described above was bead-applied to a release paper, and was left for 10 minutes under the conditions of 35° C. and 90% RH.

After 10 minutes, the steel sheet to which the primer was applied overlapped on the composition on the release paper and pressed to produce the sample for pot life evaluation. In the sample for pot life evaluation, the thickness of the composition between the release paper and the electrodeposition-coated steel sheet was 3 mm, the length of the overlapping portion of the release paper and the electrodeposition steel sheet was 100 mm, and the width of the overlapping portion between the release paper and the electrodeposition-coated steel sheet was 15 mm.

The sample for pot life evaluation produced as described above was left under conditions of 20° C. and 65% RH for 1 hour. Hereinafter, the composition in the sample for pot life evaluation is referred to as an adhesive.

Peeling Test

The hand peeling test by knife cut was performed for the sample for pot life evaluation after left for 1 hour on under conditions of 20° C. and 65% RH as described above.

Evaluation Criteria of Pot Life

As a result of the peeling test, when the adhesive was not peeled off from the sample for pot life evaluation, the pot life could be sufficiently secured and thus was evaluated to be excellent, which was represented by “good”.

When the adhesive was peeled off from the sample for pot life evaluation, the pot life could not be sufficiently secured and thus was evaluated to be poor, which was represented by “poor”.

TABLE 1 Example 1 2 3 4 5 6 7 Main agent Urethane 100 100 100 100 100 100 100 prepolymer CB 60 60 60 60 60 60 60 Calcium carbonate 40 40 40 40 40 40 40 Plasticizer 40 40 40 40 40 40 40 Metal catalyst 0.015 0.015 0.015 0.015 0.015 0.015 0.015 Organophosphorus compound (TPP) Morpholine 0.03 0.03 0.03 0.2 0.2 0.3 0.6 compound 1 (X- DM) Morpholine compound 2 (ethyl morpholine) Ether compound 1 0.02 0.09 0.15 0.15 0.003 0.05 0.02 (BL-19) Comparative morpholine compound (DMDEE) Curing Active hydrogen 1 1 1 1 1 1 1 agent compound 1 Active hydrogen compound 2 Evaluation Cycle/vibration Good Good Good Good Good Good Good composite test: adhesion Discharge test: yarn Fair Fair Fair Fair Fair Fair Fair breakage property Curing rate Good Good Good Good Good Good Good Pot life Good Good Good Good Good Good Good Example 8 9 10 11 12 13 14 Main agent Urethane 100 100 100 100 100 100 100 prepolymer CB 60 60 60 60 60 60 60 Calcium carbonate 40 40 40 40 40 40 40 Plasticizer 40 40 40 40 40 40 40 Metal catalyst 0.015 0.015 0.015 0.015 0.015 0.015 0.015 Organophosphorus compound (TPP) Morpholine 0.8 0.9 1.5 1.6 1.7 0.05 0.8 compound 1 (X- DM) Morpholine compound 2 (ethyl morpholine) Ether compound 1 0.08 0.003 0.02 0.002 0.01 0.005 0.11 (BL-19) Comparative morpholine compound (DMDEE) Curing Active hydrogen 1 1 1 1 1 1 1 agent compound 1 Active hydrogen compound 2 Evaluation Cycle/vibration Good Good Good Good Good Good Good composite test: adhesion Discharge test: yarn Fair Fair Fair Fair Poor Fair Poor breakage property Curing rate Good Good Good Good Good Poor Good Pot life Good Good Good Good Good Good Good Example 15 16 17 18 19 20 21 22 23 24 Main Urethane 100 100 100 100 100 100 100 100 100 100 agent prepolymer CB 60 60 60 60 60 60 60 60 60 60 Calcium 40 40 40 40 40 40 40 40 40 40 carbonate Plasticizer 40 40 40 40 40 40 40 40 40 40 Metal catalyst 0.015 0.015 0.015 0.015 0.015 0.015 0.015 0.015 0.015 0.015 Organophosphorus 0.03 0.95 0.1 0.1 0.1 0.1 0.1 compound (TPP) Morpholine 0.6 0.6 0.9 0.03 0.8 0.03 0.8 0.01 0.6 compound 1 (X-DM) Morpholine 1.5 compound 2 (ethyl morpholine) Ether 0.02 0.02 0.003 0.09 0.08 0.09 0.08 0.05 0.02 0.02 compound 1 (BL-19) Comparative morpholine compound (DMDEE) Curing Active 1 1 1 1 1 0.1 3 1 1 agent hydrogen compound 1 Active 1.15 hydrogen compound 2 Evaluation Cycle/vibration Good Good Good Good Good Good Good Good Good Good composite test: adhesion Discharge Test: Good Good Good Good Good Good Good Fair Fair Fair yarn breakage property Curing rate Good Good Good Good Good Good Good Fair Fair Good Pot life Good Good Good Good Good Good Poor Good Good Good Comparative Example 1 2 3 4 5 6 Main agent Urethane prepolymer 100 100 100 100 100 100 CB 60 60 60 60 60 60 Calcium carbonate 40 40 40 40 40 40 Plasticizer 40 40 40 40 40 40 Metal catalyst 0.015 0.015 0.015 0.015 0.015 0.015 Organophosphorus compound (TPP) Morpholine 0.9 0.6 0.3 compound 1 (X-DM) Morpholine compound 2 (ethyl morpholine) Ether compound 1 0.09 0.1 0.1 (BL-19) Comparative 0.1 0.6 0.1 0.6 morpholine compound (DMDEE) Curing Active hydrogen 1 1 1 1 1 1 agent compound 1 Active hydrogen compound 2 Evaluation Cycle/vibration Poor Poor Poor Poor Poor Poor composite test: adhesion Discharge Test: yarn Fair Fair Fair Poor Fair Fair breakage property Curing rate Good Poor Good Good Good Good Pot life Good Good Good Good Good Good

Details of the components described in Table 1 are as follows.

-   -   Urethane prepolymer: 500 g of polyoxypropylene diol (weight         average molecular weight of 2000), 750 g of polyoxypropylene         triol (weight average molecular weight of 5000), and 214 g of         4,4′-diisocyanatephenylmethane (molecular weight of 250) were         mixed (at this time, NCO/OH=1.8), 160 g of diisononyl phthalate         was further added thereto, and the mixture reacted while         stirring at 80° C. for 24 hours in a nitrogen gas stream to         synthesize the urethane prepolymer containing 1.95% of         isocyanate group.     -   CB: Carbon black, trade name: Niteron #200, manufactured by         Nippon Steel Carbon Co., Ltd.     -   Calcium carbonate: Heavy calcium carbonate, trade name Super SS,         manufactured by Maruo Calcium Co., Ltd.     -   Plasticizer: Diisononyl phthalate     -   Metal catalyst: Dioctyltin laurate (NEOSTANN U-810, available         from Nitto Kasei Co., Ltd.)     -   Organophosphorus compound (TPP): Triphenylphosphine, available         from Johoku Chemical Co., Ltd.     -   Morpholine compound 1 (X-DM): Dimethylaminoethyl morpholine,         trade name X-DM, available from Ciba Geigy Co., Ltd.     -   Morpholine compound 2 (ethyl morpholine): Ethyl morpholine,         available from Kanto Kagaku.     -   Ether compound 1 (BL-19): bis(dimethylaminoethyl) ether, trade         name BL-19, available from Ciba Geigy Co., Ltd.     -   Comparative morpholine compound (DMDEE): Dimorpholino         diethylether (available from San-Apro Ltd.)     -   Active hydrogen compound 1: trade name Excenol 450 ED, available         from Asahi Glass Company, Limited 450 mg KOH/g of hydroxyl         value. A compound represented by Chemical Formula (4) below         which has four hydroxy groups in 1 molecule.

In Chemical Formula (4) above, R₆ to R₉ each represent a propylene group independently, R₁₀ represents an ethylene group, and a to d each represent 1 to 10 independently.

-   -   Active hydrogen compound 2: trade name Excenol 385 SO, available         from Asahi Glass Company, Limited. 385 mg KOH/g of hydroxyl         value. A compound having six hydroxy groups in one molecule.         Polyoxypropylene polyol with sorbitol as an initiator.

As apparent from the results shown in Table 1, Comparative Example 1 containing no predetermined morpholine compound had low adhesion.

Further, Comparative Examples 2 and 3 which do not contain a predetermined morpholine compound but instead contain a compound having a plurality of morpholine rings and contain a predetermined ether compound had low adhesion.

Comparative example 4 which does not contain a predetermined an ether compound had low adhesion.

Further, Comparative Examples 5 and 6 which contain a predetermined morpholine compound and a compound having a plurality of morpholine rings and do not contain a predetermined ether compound had low adhesion.

On the contrary, the composition according to the embodiment of the present technology is excellent in adhesion.

In addition, when the composition according to the embodiment of the present technology further contains a predetermined organophosphorus compound (Examples 15 to 21), the composition had the more excellent yarn breakage property than when the composition does not contain the organophosphorus compound (Examples 1 to 14, and 22 to 24).

From the comparison of Examples 1 to 11 with Example 12, the content of the morpholine compound is from 0.02 to 1.6 parts by mass with respect to 100 parts by mass of the urethane prepolymer, and/or when in the above Chemical Formula (3), x+10y is 1.7 or less (Examples 1 to 11), the content of the morpholine compound is 1.7 parts by mass, and when x+10y is 1.8 (Example 12), the yarn breakage property was more excellent.

From the comparison of Examples 1 to 12 and 23 with Example 13, the curing rate is faster when the content of the morpholine compound and the ether compound satisfy Chemical Formula (3) above than when the content of the morpholine compound and the ether compound do not satisfy the above Chemical Formula (3) (Example 13).

From the comparison of Examples 1 to 11 and 23 with Example 14, the yarn breakage property is more excellent when the content of the morpholine compound and the ether compound satisfy the above Chemical Formula (3) (x+10y is 1.7 or less) than when the content of the morpholine compound and the ether compound do not satisfy Chemical Formula (3) above (Example 14).

From the comparison of Example 19 with Example 21, when the amount of the active hydrogen compound used was small, the pot life could be sufficiently secured, and the balance between the curing rate and the pot life was excellent. 

The invention claimed is:
 1. A polyurethane composition, comprising: a main agent; and a curing agent, wherein the main agent includes a urethane prepolymer having an isocyanate group, a morpholine compound having one morpholine ring, and an ether compound having two dimethylamino groups, the curing agent includes an active hydrogen compound having two or more active hydrogen-containing groups in one molecule, a content of the morpholine compound is from 0.02 to 1.6 parts by mass with respect to 100 parts by mass of the urethane prepolymer, and a content of the ether compound is from 0.002 to 0.16 parts by mass with respect to 100 parts by mass of the urethane prepolymer.
 2. The polyurethane composition according to claim 1, wherein the morpholine compound is dimethylaminoethyl morpholine.
 3. The polyurethane composition according to claim 1, wherein the ether compound is bis(dimethylaminoethyl) ether.
 4. A polyurethane composition, comprising: a main agent; and a curing agent, wherein the main agent includes a urethane prepolymer having an isocyanate group, a morpholine compound having one morpholine ring, an ether compound having two dimethylamino groups, and at least one organophosphorus compound selected from the group consisting of a phosphite compound, a phosphonite compound, a phosphinite compound, and a phosphine compound, and the curing agent includes an active hydrogen compound having two or more active hydrogen-containing groups in one molecule.
 5. The polyurethane composition according to claim 4, wherein a content of the organophosphorus compound is from 0.01 to 1.0 part by mass with respect to 100 parts by mass of the urethane prepolymer.
 6. The polyurethane composition according to claim 4, wherein the organophosphorus compound is triphenylphosphine.
 7. The polyurethane composition according to claim 1, wherein the active hydrogen compound contains at least a tetravalent hydroxy compound having 4 hydroxy groups in one molecule.
 8. The polyurethane composition according to claim 1, wherein a hydroxyl value of the active hydrogen compound is from 200 to 500 mg KOH/g.
 9. A polyurethane composition, comprising: a main agent; and a curing agent, wherein the main agent includes a urethane prepolymer having an isocyanate group, a morpholine compound having one morpholine ring, and an ether compound having two dimethylamino groups, the curing agent includes an active hydrogen compound having two or more active hydrogen-containing groups in one molecule, and a content of the active hydrogen compound is from 0.2 to 2 parts by mass with respect to 100 parts by mass of the urethane prepolymer. 